New acid amide azo-pigment-dyestuffs



United States Patent NEWACID AMIDE AZO-PIGMENT-DYESTUFFS Rudolf Mory,Doruach, Switzerland, assignor to Ciba Limited, Basel, Switzerland, afirm of Switzerland No Drawing. Application January 2, 1 959 Serial No.784,434

Claims, priority, application Switzerland September 7, 1956 9 Claims.01. 260-188 in which R represents an aromatic radical of the benzene ornaphthalene series, R represents an aromatic radical of the benzene ornaphthalene series in which the azogroups are in the 1:4-positions withrespect to each other, R represents a naphthalene radical in which theazo-, hydroxyl and CONH-Pyr groups occupy the 1-, 2- and 3- positionsrespectively, m and n are 1 or 2 and Pyr stands for a pyrene radical.

The invention also provides a process for the manufacture of the abovepigments, which are carboxylic acid amide derivatives of azo-dyestufis,wherein a carboxylic acid halide which is free from water-solubilizinggroups and corresponds to the formula in which R, and R have themeanings given above, R represents a naphthalene radical in which theazo-, hydroxyl and carboxylic acid halide groups occupy the l-, 2- and3-positions respectively and m and n are 1 or 2, is reacted with amonoamino-pyrene which is free from Water-solubilizing groups.

The starting materials used in the above process are free fromwater-solubilizing groups such as sulfonic acid groups, sulfonamide,methylsulfone and carboxylic acid groups. As the aminopyrene startingmaterials there may be mentioned, more especially, 3-aminopyrene. Therealso come into consideration, however, aminopyrenes which aresubstituted in the pyrene nucleus, for example, which contain anacylamino group.

The azo-carboxylic acids, from which the acid halides of the aboveformula are manufactured, may be obtained (a) by coupling an aromaticamine of the formula a norm or 111 COOH with a middle component of theformula RgNHg in which R and R have the meanings given above,diazotizing the aminomonoazo-dyestuif so obtained and coupling with a2:3-hydroxynaphthoic acid, or (b) by coupling a compound of the formulaCOOH with a 2:3-hydroxynaphthoic acid.

As amines of the formula R NH there come into considerationwater-solubilizing group-free-amines of the naphthalene series, as forexample, l-amino-naphthalene, but especially amino-benzenes. As examplesthere may be mentioned: unsubstituted aniline, nuclear halogenatedanilines as, for example, orth0-, paraor meta-chloraniadvantageouslycarried out in inert organic solvents such line, 2:5-dichloraniline,3:4:5-t1ichloraniline, para-bromaniline, nitro-anilines such as ortho-,paraor meta-nitroaniline, alkoxy-anilines as, for example, orthoandparamethoxy-aniline, nuclear alkylated anilines such as toluidines,meta-xylidine, halogeno-alkylanilines such as 3-tri fluoromethyl anilineor 3:5-di-(tri-tluoro-methyl-aniline, phenyl anilines containing'afunctionally converted carboxylic group, for example,-a carboxylic acidester group, cyano-group or carboxylic acid-phenyl amide group. As-

compounds containing such groups the following repre-L sentatives may bementioned: aniline-B-carboxylic acid methyl ester,aniline-3:5-dicarboxylic acid-dimethyl ester,

3-cyanoaniline, 3- or 4-aniline carboxylic acid anilide.

Furthermore, there come into consideration anilines containing differentsubstitutents as, for example, 2-chloro- S-methyl-aniline,4-chloro-2-methylaniline, 2-methyl-5- chloroaniline,2-chloro-4-nitroaniline, 2-chloro-5-trifluoro methylaniline,2-nitro-4-chloroaniline, 4--chloro-2-methoxyaniline,2-chloro-4-methcxyaniline, 4-chloro-2-methoxy-5-methylaniline,2-ni-tro-4-methyl aniline, 4- or 5- nitro-2-methylaniline,4-nitro-2-methoxyaniline and 4- chloro-2 5 -dimethoxyaniline.

As carboxylic acid group-containing amines of the formula 00011 theremay be mentioned:

As middle components of the formula R NH there come into considerationwater solubilizing group-free-.

amines of the benzene or naphthalene series which couple in thepara-position to the amino group, for example, 1- arninonaphthalene,l-amino-S-chIoronaphthalene, but above all anilines, as for exampleaniline, halogeno-anilines, as for example 2-chloroaniline,alkoxy-anilines, as for example, 2 -methoxyor 2-ethoxy-aniline,2:5-dimethoxy-aniline or 2:5-diethoxy-aniline, nuclear alkylated,anilines, as for example, 2-methoxy-S-rnethyl-anilines, 2-chloro-S-methyl aniline or 2-chloro-5-methoxy-aniline.

As final coupling components there are used 2:3-hydroxynaphthoic-acids,which, if desired, may be substituted in the benzene ring which is freefrom the carboxylic acid group, for example, by a halogen atom or analkoxyor alkylgroup. Advantageously there is used, however, as a resultof its easy accessibility, the unsubstituted 2:3-hydroxynaphthoic acid.

The azo-carboxylic acids are treated with agents which enable carboxylicacids to be converted into their halides, for example, the chlorideorbromide, especially with phosphorus halides such as phosphoruspentabromide or ph0sphorus trichloride or phosphorus pentachloride,phosphorusoxyhalides, and especially with thionyl chloride.

The treatment with such acid-halogenating agents is Patented Apr. 12,1959' as chlorobenzene, as for 3 example, monoor dichlorobenzene,toluene, xylene or nitrobenzene.

In the preparation of thecarboxylic acid halides it is advantageous ifthe azo-compounds which are obtained in an, aqueous medium are firstdried by boiling in an organic solvent which forms an azeotrope withWater to free them from Water- This azeotropic drying can, if desired,be carried out immediately before the treatment with the acidhalogenating agents.

"The products of the invention are valuable, new blue toBordeaux-colored pigments which are distinguished by an especially goodcolor-strength and are particularly suitable for the coloring ofpolyvinyl compounds, for'example, by rolling them into polyvinyl foils,and are also distinguished by especially good resistance to light and tomigration and also resistance to temperature and to V solvents. I g Theyare also valuable for the so-called pigment print-- ing, that is to say,for printing methods which depend upon fixing the pigment by means of asuitable adhesive agent, such as casein, heat-hardenable syntheticresins, especially urea-. or melamine-formaldehyde condensationproducts, polyvinyl chloride or polyvinyl acetate solutions or emulsionsor other emulsions (for example oil-in-water or water-in-oil emulsions),to a substratum, especially to textile fibers, but also to flatstructures, such as paper (for example, wall-paper) or to glass-fiberfabrics. The pigments of the invention can also be used for otherpurposes, for example for the coloring of artificial silk and viscose orcellulose ethers and esters or super-polyamides or super-polyurethanesby incorporation in finely divided form in the spinning composition, aswell as for the manufacture of colored lacquers or lacquer-formers,solutions and products from acetylcellulose, nitro-cellulose, natural orsynthetic resins, such as polymerizationor condensation resins, forexample, aminoplasts, phenoplasts, polystyrene, polyethylene,polyacrylate, rubber, casein, silicon and silicone resins. Furthermorethey may be advantageously used in the manufacture of colored pencils,cosmetic preparations or laminates.

Preparations which contain the pigments in finely divided form can beobtained in known manner by intensive mechanical treatment, for example,by passing between rollers or by means of suitable kneading apparatus.For this there is chosen for the dispersion and the intensive working asuitable medium according to the desired purpose in view, for example,for the manufacture of aqueous dispersible preparations there may beused sulfite waste liquor or naphthylmethane-disulfonic acid salts, andfor the manufacture of acetate-artificial silk spinning preparationsthere is used acetyl cellulose mixed with a small quantity of solvent.

In consequence of the especially good physical form in which theproducts of the invention are generally obtained, and in view of theirchemical inertness and good resistance to temperature, they can normallybe readily distributed in the compositions or preparations of thementioned kind and advantageously in a short period of time, since thesecompositions or preparations do not yet occupytheir definite form. Therequired shaping meth ods', such as spinning, pressure moulding,hardening, casting or sticking or other methods can be carried outdirect- 1y the presence of the above pigments without hindrance toeventual chemical reactions of the substrata, such as furtherpolymerization or condensation.

The following examples illustrate the invention, the parts being byweight unless otherwise stated:

7 Example 1 v A mixture of 50.9 parts of the disazo-dyestufi carbqxylicacid, which had been obtained by coupling diazo-; tized1-amino-2:S-dichlorobenzene with I-amino-S-methyl-2 -methoxybenzene,diazotizing again the amino-monoazo-dyestufi so obtained and couplingwith 2:3-hydroxy,-

'zene was dehydrated completelyby distillation with 50 parts by volumeof the organic solvent. To the cold mixture there were added 0.8 part byvolume of dimethyl formamide and 14.2 parts by volume of thionylchloride and the mixture was heated for an hour at 130 to 140 C. Themixture wasthen allowed to cool and the dymtufi chloride which separatedin coarse crystalline needles was washed with a quantity of coldchlorobenzene, then with petroleum ether and dried in vacuo at roomtemperature. The chloride obtained was a dark crystalline powder havinga bronze lustresurface.

A mixture of 52.75 parts of this chloride, 22.8 parts of 3-aminopyrene,1750 parts by volume of chlorobenz'ene and 8 parts by volume of pyridinewere heated for 16 hours at 130- 140". -C. The pigment separating astiny, curved needles was filtered hot and purified by washing withboiling chlorobenzene, boiling alcohol and boiling water. After dryingin vacuo at 50 to 60 C. the pigment was obtained as a violet, softgranular powder. It was completely insoluble in boiling chlorobenzeneand boiling dimethyl formarnide, and colored polyvinyl chlo- 1 ride aviolet tint of very; good color strength and having very g'oodresistanceto migration and light.

By using l-amino-Z:S-dimethylbenzene instead of lamino-S-methyl-2rnethoxybenzene as'middle component of the starting dyestufis, there canbe obtained in the. above manner a pigment coloring polyvinyl chloridefoils. red-violet and which has good resistance to migration and tolight.

By using l-amino-Z:S-diethoxybenzene as middle component of the startingdyestuffs, there can be obtained a pigment which colors polyvinylchloride foils a blue tint and which also hasvery good properties.

By using 3-acetylamino:S-amino-pyrene instead of 3- aminopyrene in thesecond paragraph there is obtained a pigment coloring polyvinyl chloridefoils somewhat more reddish violet shades.

Examples 2 v A mixture of 15.1 parts of the disazo-dyestuff-dicarboxylicacid which is obtained by coupling diazotized 1-amino2-chlorobenzene-S-carbOxylic acid with l-arnino- 2:5-dimethylbenzene,diazotizing again the aminomonoazo-dyestufi so obtained and couplingwith 2:3-hydroxybenzene, then. with petroleum ether and was dried invacuo at room temperature.

15.8 parts of this chloride in admixture with 14.3 parts of3-aminopyrene, 5 parts by volume of pyridine and 400 parts by volume ofchlorobenzene' were heated for 16 hours at 130-140 C. Thedifiicultly-soluble pigment which separated was filtered hot and washedwith boil ing chlorobenzene, boiling alcohol and boiling water. Thedried product was a violet, soft granular powder which was completelyinsoluble in boiling chlorobenzene and boiling dimethyl formamide. Thispigment colored polyvinyl chloride at red-violet tint of very good colorstrength and having very good resistance tomigration' andto light. r

. The following table shows further pigments which were obtained by themethod given in the above example, by coupling the, diazo-compounds ofeach of the amines mentioned in column 1 with the correspondingmiddle-component shown in column 2, diazotizing the aminoazo-dyestufi soobtained, coupling with 2:3-hynaphthoic acid, and 500 parts by volume ofchloroben- 5 aminopyrene. Column 3 shows the color tint which isobtained by coloring polyvinyl chloride with the pigment.

Example 3 36.6 parts of the dyestufi obtained by coupling diazotized3-amino-4-methoxy-benzoic acid with 2:3-hydroxynaphthoic acid are mixedwith 1000 parts by volume of chlorobenzene, 1.6 parts by volume ofdimethylformamide and 19.9 parts by volume of thionyl chloride andheated for one hour at 130140 C. with stirring. After cooling thereaction mixture, the dicarboxylic acid chloride of the dyestufi,consisting of thin yellow-red needles, is isolated by filtration anddried in vacuo at to 60 C.

36.3 parts of the above chloride are heated in 1000 parts by volume ofortho-dichlorobenzene at 100 C. with stirring. A hot solution (about 100C.) of 43 parts of S-aminopyrene and 14.4 parts by volume of pyridine in300 parts by volume of ortho-dichlorobenzene is added to the mixture.The whole is stirred for 20 hours at 140-150 C. The pigment formed isfiltered at 120 C., washed with hot ortho-dichlorobenzene, hot alcoholand hot water and dried in vacuo at 50 to 60 C. The pigmerit dyestuif isa blue-red powder which is very sparingly soluble in organic solventsand colors polyvinyl chloride foils ruby red tints which are fast tolight and migration.

The product obtained has the following formula When6-bromo-2:3-hydroxynaphthoic acid is used instead of2:3-hydroxynaphthoic acid, a pigment is obtained which colors polyvinylchloride somewhat more bluish tints of similarly good fastness to lightand migration.

Example 4 65 parts of polyvinyl chloride, 35 parts of dioctyl phthalateand 0.2 part of the pigment obtained according to Example 1 were mixedtogether and then rolled on a two-roll-calendar mill for 7 minutes atThere was obtained a violet colored foil having very good resistance tolight and migration.

What is claimed is:

1. An azo-pigment-dyestufi which is free from watersolubilizing groupsand which corresponds to the formula ---[0 ON H Pyrh-r CONHPyr in whichR represents a benzene radical, R represents a carbocyclic aromaticradical having at most 10 nuclear carbon atoms in which the azogroupsare in 1:4-position with respect to each other, Pyr stands for a3-pyrene radical, and m and n are whole numbers of at most 2 and n+m isat least 3.

2. An azo-pigment-dyestufi which is free from Watersolubilizing groupsand which corresponds to the formula CONHPyr in which R represents abenzene radical, R represents a carbocyclic aromatic radical having atmost 10 nuclear carbon atoms in which the azo-groups are in 1:4-positionwith respect to each other, Pyr stands for the 3-pyreneradical and n isa whole number of at most 2.

3. An azo-pigment dycstuif which is free from watersolubilizing groupsand which corresponds to the formula ll 1=NR:C ONHPyr in which Rrepresents a benzene radical, Pyr stands for the 3-pyrene-radical, X fora member selected from the group consisting of a hydrogen and a bromineatom.

4. The azo-pigment dyestufi of the formula 5. The azo-pigment dyestuftof the formula 6. The azb-pigment flyestufl of the formula OCH:

7. The-azmpigment dyestufi of the formula OH OCH:

OCH:

8. The ale-pigment 'dyestuff of the formula 9. The azo-pigment dyestuflof the formula OCHa References Cited-in the file of this patent UNITEDSTATES PATENTS '2,163;074 Thomas et a1 Jan. 20, 1939 2,170,372 Kern Aug.22,1939

1. AN AZO-PIGMENT-DYESTUFF WHICH IS FREE FROM WATERSOLUBLIZING GROUPSAND WHICH CORRESPONDS TO THE FORMULA